Chiral Transition Metal Oxides: Synthesis,Chiral Origins,and Perspectives

Transition metal oxides (TMOs) consist of a series of solid materials, exhibiting a wide variety of structures with tunability and versatile physicochemical properties. Such a statement is undeniably true for chiral TMOs since the introduction of chirality brings in not only active optical activities but also geometrical anisotropy due to the symmetry-breaking effect. Although progressive investigations have been made for accurately controlled synthesis and relevant explanations on the chirality origin of such materials, the overall field of chiral TMOs is still in its infancy with adequate space for interdisciplinary communications and development. Herein, therefore, recent advances in both experimental phenomena and theoretical calculations in this area are reviewed, to elucidate the underlying chiral origin with respect to their fabrications process, triggering new insights for further evolution of this field.     

Enantiomeric Control of Intrinsically Chiral Nanocrystals

The chiral aspect of inorganic crystals that crystallize in chiral space groups has been largely ignored until recently, partly due to difficulties in characterizing the chiroptical properties of bulk crystals, and also due to the difficulty in separating (sub)micrometer-scale chiral crystal enantiomers. In recent years, the colloidal synthesis of intrinsically chiral nanocrystals (NCs) of several chiral inorganic compounds with significant enantiomeric excess has been demonstrated. This is achieved through the use of chiral molecular ligands, which bind to the atomic/ionic components of the crystals, preferentially forming one crystal enantiomorph. Here, recent progress on several aspects of these NCs is described, including the connection between ligand structure and its ability to direct NC handedness, chiral amplification in the synthesis leading to enantiopure NC samples, spontaneous symmetry breaking, the formation of NCs with chiral shapes, the connection between lattice and shape chirality and mixed contributions of atomic-scale and shape chirality to the chiroptical properties.     

A Generalized Surface Chalcogenation Strategy for Boosting the Electrochemical N2 Fixation of Metal Nanocrystals

Electrocatalytic nitrogen reduction reaction (NRR) is a promising process relative to energy-intensive Haber–Bosch process. While conventional electrocatalysts underperform with sluggish paths, achieving dissociation of N₂ brings the key challenge for enhancing NRR. This study proposes an effective surface chalcogenation strategy to improve the NRR performance of pristine metal nanocrystals (NCs). Surprisingly, the NH₃ yield and Faraday efficiency (FE) (175.6 ± 23.6 mg h^–1 g^–1_Rh and 13.3 ± 0.4%) of Rh-Se NCs is significantly enhanced by 16 and 15 times, respectively. Detailed investigations show that the superior activity and high FE are attributed to the effect of surface chalcogenation, which not only can decrease the apparent activation energy, but also inhibit the occurrence of the hydrogen evolution reaction (HER) process. Theoretical calculations reveal that the strong interface strain effect within core@shell system induces a critical redox inversion, resulting in a rather low valence state of Rh and Se surface sites. Such strong correlation indicates an efficient electron-transfer minimizing NRR barrier. Significantly, the surface chalcogenation strategy is general, which can extend to create other NRR metal electrocatalysts with enhanced performance. This strategy open a new avenue for future NH₃ production for breakthrough in the bottleneck of NRR.     

Shape Control of Colloidal Metal Nanocrystals

Colloidal metal nanoparticles are emerging as key materials for catalysis, plasmonics, sensing, and spectroscopy. Within these applications, control of nanoparticle shape lends increasing functionality and selectivity. Shape‐controlled nanocrystals possess well‐defined surfaces and morphologies because their nucleation and growth are controlled at the atomic level. An overall picture of shaped metal particles is presented, with a particular focus on solution‐based syntheses for the noble metals. General strategies for synthetic control are discussed, emphasizing key factors that result in anisotropic, nonspherical growth such as crystallographically selective adsorbates and seeding processes.     

Two‐Dimensional Arrays of Transition Metal Nitride Nanocrystals

The synthesis of low‐dimensional transition metal nitride (TMN) nanomaterials is developing rapidly, as their fundamental properties, such as high electrical conductivity, lead to many important applications. However, TMN nanostructures synthesized by traditional strategies do not allow for maximum conductivity and accessibility of active sites simultaneously, which is a crucial factor for many applications in plasmonics, energy storage, sensing, and so on. Unique interconnected two‐dimensional (2D) arrays of few‐nanometer TMN nanocrystals not only having electronic conductivity in‐plane, but also allowing transport of ions and electrolyte through the porous nanosheets, which are obtained by topochemical synthesis on the surface of a salt template, are reported. As a demonstration of their application in a lithium–sulfur battery, it is shown that 2D arrays of several nitrides can achieve a high initial capacity of >1000 mAh g^?1 at 0.2 C and only about 13% degradation over 1000 cycles at 1 C under a high areal sulfur loading (>5 mg cm^?2).     

ZnS纳米晶的无膦法制备及表征

以硬脂酸锌和硫脲作为锌源与硫源,无膦绿色溶剂油酸（OA）作为单一的反应溶剂和包裹剂,利用一步合成路线制备ZnS纳米晶,实验结果表明,该方法制备出的ZnS纳米晶为立方闪锌矿结构,ZnS纳米晶的形成过程是典型的Ostwald熟化过程。改变反应条件不仅可以调控纳米晶的成核和生长,而且对其光学性能也有重要影响。     

纤维素纳米晶手性向列液晶在颜色防伪中的应用

目的介绍纤维素纳米晶(Cellulose Nanocrystal,CNC)手性向列液晶的形成原理与特征,以及该结构的调控方法,包括螺距和折射率的调控,最后总结纤维素纳米晶及其衍生材料在颜色防伪中的应用。方法归纳CNC手性向列液晶的形成机理方法,如硫酸水解结合蒸发诱导自主装法以及以CNC为手性模板与其他溶液共混制备法。最后总结国内外CNC手性向列液晶在颜色防伪中的研究现状,并简要讨论纤维素纳米晶在颜色防伪的未来发展趋势。结论纤维素纳米晶,具有绿色环保、来源丰富、合成工艺简单等特点,在一定条件下能形成手性向列液晶结构,具有独特的光学性质并呈现出结构色,可应用于颜色防伪。     

Glycothermal法制备钛酸锶钡纳米晶的研究

采用Glycothermal法制备了尺寸分布窄的准球形钛酸锶钡纳米晶. 利用XRD、拉曼光谱以及TEM对合成纳米晶结构及形貌进行了测定与表征, 研究了Glycothermal法制备BST纳米晶过程中醇-水比、温度和液相中Ba/Sr比等因素对产物组成、晶体结构、晶粒尺寸与结晶性的影响规律. 结果表明: 利用Glycothermal法, 可在无矿化剂的条件下制备出单分散性好的BST纳米晶.     

Endowing Perovskite Nanocrystals with Circularly Polarized Luminescence

Perovskite nanocrystals are attracting great interest due to their excellent photonic properties. Here, through a supramolecular self‐assembly approach, the perovskite nanocrystals (NCs) with a novel circularly polarized luminescence (CPL) are successfully endowed. It is found that the achiral perovskite NCs can coassemble with chiral gelator in nonpolar solvents, in which the gelator molecules modify the surface of the perovskite NCs. Through such cogelation, the molecular chirality can transfer to the NCs resulting in CPL signals with a dissymmetric factor (g_lum) up to 10^?3. Furthermore, depending on the molecular chirality of the gelator, the CPL sense can be selected and the mirror‐imaged CPL is obtained. Such gels can be further embedded into the polymer film to facilitate flexible CPL devices. It is envisaged that this approach will afford a new insight into the designing of the functional chiroptical materials.     

Integration of Optical Surface Structures with Chiral Nanocellulose for Enhanced Chiroptical Properties

The integration of chiral organization with photonic structures found in many living creatures enables unique chiral photonic structures with a combination of selective light reflection, light propagation, and circular dichroism. Inspired by these natural integrated nanostructures, hierarchical chiroptical systems that combine imprinted surface optical structures with the natural chiral organization of cellulose nanocrystals are fabricated. Different periodic photonic surface structures with rich diffraction phenomena, including various optical gratings and microlenses, are replicated into nanocellulose film surfaces over large areas. The resulting films with embedded optical elements exhibit vivid, controllable structural coloration combined with highly asymmetric broadband circular dichroism and a microfocusing capability not typically found in traditional photonic bioderived materials without compromising their mechanical strength. The strategy of imprinting surface optical structures onto chiral biomaterials facilitates a range of prospective photonic applications, including stereoscopic displays, polarization encoding, chiral polarizers, and colorimetric chiral biosensing.     

Small Adsorbate-Assisted Shape Control of Pd and Pt Nanocrystals

The shape control of noble metal nanocrystals is crucial to their optical properties and catalysis applications. In this Progress Report, the recent progress of shape-controlled synthesis of Pd and Pt nanostructures assisted by small adsorbates is summarized. The use of small strong adsorbates (e.g., I⁻, CO, amines) makes it possible to fabricate Pd and Pt nanostructures with not only well-defined surface structure but also morphologies that have not been achieved by other synthetic strategies. The roles of small adsorbates in shape control of Pd and Pt nanocrystals are discussed in the Report. Also presented in the Report are unique optical and catalytic properties of several Pd and Pt nanostructures (e.g., ultrathin Pd nanosheets, concave Pt octapod, concave Pd tetrahedra), as well as their bioapplications, to demonstrate the power of using small strong adsorbates in the shape control of Pt and Pd nanostructures.     

螺旋形手征碳纤维的微波介电特性

研究了线圈状和麻花状两种典型螺旋形手征碳纤维以及直线形碳纳米管在8.2-12.4GHz的微波介电特性.螺旋形手征碳纤维通过催化化学气相沉积法制备,直线形碳纳米管用催化裂解浮游法以苯为碳源制备.螺旋形手征碳纤维与石蜡复合体的介电常数的实部(ε′)和虚部(ε″)比直线形碳纳米管与石蜡复合体的小,但线圈状螺旋形碳纤维的介电损耗角正切(tgδ=ε″/ε′)却明显偏大,线圈状和麻花状螺旋形碳纤维的tgδ分别为0.77—0.80和0.47—0.53,直线形碳纳米管的tgδ为0.45-0.77.螺旋形碳纤维与微波作用时的手征特性是导致其tgδ增大的主要原因,螺旋形手征碳纤维对微波的吸收与其自身的形状和尺寸密切相关,所以线圈状螺旋形碳纤维的tgδ比麻花状的大得多,探讨了螺旋形手征碳纤维与微波的作用机理,螺旋形手征碳纤维是一种非常有发展前景的微波吸收材料.     

Localized Surface Plasmon Resonance Enhanced Light Absorption in AuCu/CsPbCl3 Core/Shell Nanocrystals

Localized surface plasmon resonance (LSPR) is shown to be effective in trapping light for enhanced light absorption and hence performance in photonic and optoelectronic devices. Implementation of LSPR in all-inorganic perovskite nanocrystals (PNCs) is particularly important considering their unique advantages in optoelectronics. Motivated by this, the first success in colloidal synthesis of AuCu/CsPbCl₃ core/shell PNCs and observation of enhanced light absorption by the perovskite CsPbCl₃ shell of thickness in the range of 2–4 nm, enabled by the LSPR AuCu core of an average diameter of 7.1 nm, is reported. This enhanced light absorption leads to a remarkably enhanced photoresponse in PNCs/graphene nanohybrid photodetectors using the AuCu/CsPbCl₃ core/shell PNCs, by more than 30 times as compared to the counterparts with CsPbCl₃ PNCs only (8–12 nm in dimension). This result illustrates the feasibility in implementation of LSPR light trapping directly in core/shell PNCs for high-performance optoelectronics.     

Construction of Chiral,Helical Nanoparticle Superstructures: Progress and Prospects

Chiral nanoparticle (NP) superstructures, in which discrete NPs are assembled into chiral architectures, represent an exciting and growing class of nanomaterials. Their enantiospecific properties make them promising candidates for a variety of potential applications. Helical NP superstructures are a rapidly expanding subclass of chiral nanomaterials in which NPs are arranged in three dimensions about a screw axis. Their intrinsic asymmetry gives rise to a variety of interesting properties, including plasmonic chiroptical activity in the visible spectrum, and they hold immense promise as chiroptical sensors and as components of optical metamaterials. Herein, a concise history of the foundational conceptual advances that helped define the field of chiral nanomaterials is provided, and some of the major achievements in the development of helical nanomaterials are highlighted. Next, the key methodologies employed to construct these materials are discussed, and specific merits that are offered by each assembly methodology are identified, as well as their potential disadvantages. Finally, some specific examples of the emerging applications of these materials are discussed and some areas of future development and research focus are proposed.     

Supramolecular Chiral Nanoarchitectonics

Exploration of molecular functions and material properties based on the control of chirality would be a scientifically elegant approach. Here, the fabrication and function of chiral-featured materials from both chiral and achiral components using a supramolecular nanoarchitectonics concept are discussed. The contents are classified in to three topics: i) chiral nanoarchitectonics of rather general molecular assemblies; ii) chiral nanoarchitectonics of metal–organic frameworks (MOFs); iii) chiral nanoarchitectonics in liquid crystals. MOF structures are based on nanoscopically well-defined coordinations, while mesoscopic orientations of liquid-crystalline phases are often flexibly altered. Discussion on the effects and features in these representative materials systems with totally different natures reveals the universal importance of supramolecular chiral nanoarchitectonics. Amplification of chiral molecular information from molecules to materials-level structures and the creation of chirality from achiral components upon temporal statistic fluctuations are universal, regardless of the nature of the assemblies. These features are thus surely advantageous characteristics for a wide range of applications.     

功能氧化物纳米晶的液相法制备

对适用于制备有序结构纳米功能材料或器件的功能性氧化物纳米晶的液相法制备技术的最新研究进展进行了综述,从晶粒成核生长的物理化学原理出发,分析了各种制备方法的特点,并在此基础上指出了高分散、单一尺寸和形状可控的功能性氧化物纳米晶制备研究中仍需解决的问题和发展的方向.